Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

胶州湾流速场的声层析反演研究

采用结合匹配法和经验正交函数法的射线声层析反演方法,针对流场水平分布不均匀特点,使用距离等效分段方法对反演算法进行改进,利用三个断面声层析数据,对胶州湾口潮流场的垂直和水平分布进行反演。与传统方法比较,大大降低与实测流速垂直分布间的偏差,平均偏差小于0.02 m/s,流场垂直分布间的相关系数提高到0.85以上。分析了声传播断面上不同的流场结构,以及涨潮期间在胶州湾团岛附近出现的涡流现象,并计算得到湾口海水流量变化。结果表明,改进的射线声层析反演方法可有效地用于水平分布不均匀流场监测,仅采用少量声学观测站位,即可获得大范围的复杂流场三维信息,有利于近海海洋资源开发、海洋环境保护和船舶航行安全。     

GGR Biennial Review: Key Advances in Secondary Ion Mass Spectrometry in the Geological Sciences during the Period 2008–2009

Secondary ion mass spectrometry (SIMS or ion microprobe) remains one of the most powerful techniques in the analytical geochemist’s toolkit. The key strength of SIMS is its capacity to provide trace element and isotope data at sampling sizes which are not approached by other methods. As compared with the main competing technique of laser ablation-ICP-MS, SIMS commonly provides a total sampling mass some 10 to 500 times smaller; this feature can be the deciding factor as to whether an analytical objective is technically achievable. Additional strengths of SIMS lie in the areas of depth profiling and trace element imaging. Though perhaps not as commonly used in the geosciences, these two operational modes represent unique capabilities of SIMS.     

Analytical Developments in Secondary Ion Mass Spectrometry 2003

This annual review of secondary ion mass spectrometry (SIMS) highlights significant progress in the application of the technology for the following areas: U-Pb geochronology (notably in the fields of reference material zircons), sources of uncertainty during analysis and secondary ion yields. Major publications introduced a new zircon reference sample and dealt with an intercomparison study of a suite of established calibrators, some of which have been shown to have certain limitations. Another publication claimed that the principal uncertainty in U-Pb dating is related to variations in the Pb and U relative emission yields over a complete analytical session. 2003 saw the introduction of an automated particle identification procedure applied to the analysis of a chondritic meteorite, as well as new geometries of SIMS hardware (NanoSIMS) and techniques (time-of-flight SIMS). NanoSIMS allows a two to three order of magnitude reduction in sampling volume as a result of a reduced beam diameter, and time-of-flight SIMS allows the study of sample surfaces, and can provide data for elements concurrently.     

Isotope Ratio Determination in the Earth and Environmental Sciences: Developments and Applications in 2003

This annual review documents developments and applications in the field of isotope ratio determination, as reflected in the literature for the Earth and environmental sciences for the year 2003. Particular emphasis is placed upon the relationship between the two dominant analytical techniques-thermal ionisation mass spectrometry (TIMS) and multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS)-and the rapidly changing nature of their roles in isotope analysis. Additionally, the review covers developments in single-collector ICP-MS and TOF technologies, new sample preparation procedures and the characterisation of isotopic reference materials, together with fundamental investigations of mass spectrometer performance.     

FIB-TOF-SIMS联用技术在矿物学研究中的应用

基于聚焦离子束扫描电子显微镜的飞行时间二次离子质谱联用技术同时具备了聚焦离子束高空间分辨率以及飞行时间二次离子质谱轻元素、同位素分析以及较低的元素检出限的优势。可以实现:扫描电镜下原位分析H、Li、Be、B等轻元素;元素分布的纳米级横向空间分辨率;元素三维空间分布。能够同时得到纳米级矿物的形貌、元素组成以及元素空间分布信息,该技术在地学领域有广阔的应用前景。     

Fast computation of arrival times in heterogeneous media

We continue the work that was initiated in (K. H. Karlsen, K.-A. Lie, and N. H. Risebro. A fast marching method for reservoir simulation. Comp. Geo., 4(2) (2000)185–206) on a marching method for simulating two-phase incompressible immiscible flow of water and oil in a porous medium. We first present an alternative derivation of the marching method that reveals a strong connection to modern streamline methods. Then, through the study of three numerical test cases we present two deficiencies: (i) the original marching algorithm does not always compute the correct solution of the underlying difference equations, and (ii) the method gives largely inaccurate arrival times in the presence of large jumps within the upwind difference stencil. As a remedy of the first problem, we present a new advancing-front method, which is faster than the original marching method and guarantees a correct solution of the underlying discrete linear system. To cure the second problem, we present two adaptive strategies that avoid the use of finite-difference stencils containing large jumps in the arrival times. The original marching method was introduced as a fast tool for simulating two-phase flow scenarios in heterogeneous formations. The new advancing-front method has limited applicability in this respect, but may rather be used as a fast and relatively accurate method for computing arrival times and derived quantities in heterogeneous media.     

三疣梭子蟹低盐适应相关的SNP开发

盐度是影响三疣梭子蟹人工繁育非常重要的一个环境因素,抗低盐品系的三疣梭子蟹受到水产养殖界的广泛喜爱。分子标记辅助育种可以大大加快良种选育和性状改良的的过程,目前作为第三代的分子标记技术的SNP,广泛应用到三疣梭子蟹耐低盐品系选育过程中。本实验室已有的研究中,通过不同群体分别在盐度11和33下的基因表达差异,构建的比较转录组学数据中总共包含了615条与低渗调节相关的基因片段。为了发掘三疣梭子蟹与低盐适应相关SNP,本研究基于三疣梭子蟹比较转录组学数据研究结果,筛选出低盐调节相关候选基因片段50条,设计引物进行PCR扩增,共得到总长为18511 bp的DNA片段。通过直接测序法在低盐相关片段上发现了85个SNP位点,分布频率为0.46/100 bp,其中转换突变的比例为81%,颠换突变的比例为19%,转换的比例远远大于颠换,符合“transition bias”原理。C/T或G/A突变所占比例为55%;G/T或C/A比例为26%,A/T突变所占比例为12%,G/C突变比例为7%。通过飞行质谱法,在三疣梭子蟹低盐适应性状分离群体中各成功分型了23个SNP位点。通过卡方检验分析发现,8个SNPs与低盐适应显著相关（P<0.05）。其中有三个关联性SNP位点位于表皮蛋白基因上,有三个SNP位点位于三个新基因上,其他两个SNP位点分别位于水通道蛋白和氯离子通道蛋白基因上。这些标记的开发为三疣梭子蟹耐低盐新品种选育方法的建立奠定了良好的基础。     

利用飞行时间质谱初步分析苯酚水相光化学反应的产物分布特征

近年的实验室模拟和野外观测研究表明,酚类化合物的水相反应(aqueous-phase reaction)对环境二次有机气溶胶(secondary organic aerosol,SOA)的形成具有重要的贡献,因此探讨酚类化合物光化学过程中的演化特征有助于深化二次气溶胶形成的科学认识。本文以苯酚为研究对象,利用大气压喷雾电离(ESI)-飞行时间质谱(TOF-MS),对其在水相光化学反应下的产物分布特征进行了初步探讨。水相光照实验通过直接光解(无添加氧化剂)和光氧化反应(添加H_2O_2)两种情况进行。结果表明,两种方式进行的水相光化学反应均可能生成一系列的低聚物、羟基化化合物以及其他多官能团含氧产物。在m/z 150～400的区间内,添加H_2O_2的光氧化反应产物的分子式种类(150种)明显多于直接光解的形成产物(60种),但直接光解形成的高分子量产物(如低聚物等)离子丰度明显高于光氧化反应,直接光解的产物中可观察到四聚体化合物的生成;同时,水相光反应的产物在紫外-可见光波段内具有明显的光吸收增强特征。由此推断在大气中,以苯酚为代表的酚类化合物进入大气水相环境(云、雾水和气溶胶液态水)中发生的光化学过程对大气吸光性有机物或气溶胶的形成具有贡献作用。     

Statistical analysis of signal measurement in time-of-flight cameras

Three-dimensional imaging systems have evolved significantly in the last two decades due to increase in demand for tasks in the field of close range photogrammetry. The fast and growing need of 3D imaging devices has given rise to range image technology, especially time-of-flight (TOF) cameras, that provide direct measurement of distance between the camera and the targeted surface. A significant advantage of TOF devices over traditional range data sensors is their capability to provide frame rate range data over a full image array. In phase shift TOF cameras, phase shift sampling of the received signal is used to measure amplitude, phase and the offset (intensity) of the received signal. As a result, the quality of the measurement of these sensors depends heavily on signal-to-noise (SNR) of the incoming signal and the subsequent processing algorithms. A detailed understanding of the statistical distributions of the measurement parameters is crucial for accurate distance measurement analysis especially in low SNR scenarios. In this paper, we provide explicit noise models for the three parameters of amplitude, phase and intensity. The proposed stochastic model helps in investigating the effect of noise on signal and classifying range data reliability in TOF cameras. The model is used for prediction of errors in a TOF camera under various SNR conditions. Experimental verification confirms the validity of the model using real data for range error classification under different noise conditions.